CN105107547B - High hydrophobicity high temperature resistant solid acid catalyst - Google Patents
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Abstract
The invention discloses a kind of high hydrophobicity high temperature resistant solid acid catalyst, it is using the mesopore molecular sieves of SBA 15 as carrier, after successively modifying it twice using phenyltrimethoxysila,e and propyl trimethoxy silicane, then with chlorosulfonic acid carries out sulfonation and handles to produce solid acid catalyst finished product.Solid acid catalyst produced by the present invention is convieniently synthesized, while modifying the molecular sieves of SBA 15, maintains order mesoporous regular texture and higher specific surface area, improves the decentralization of active site, so as to add catalytic efficiency；Firmly it is strapped in by acidic-group in meso-hole structure, effectively prevent loss of active component, improves the stability of catalyst.Handled by surface hydrophobic, be conducive to the acid catalyzed reaction of organic compound；High temperature resistant, hydrophobicity is strong, has a wide range of application, and technological operation is interval wide, is easy to produce control；Non-corrosiveness, it is environmentally safe；Raw material is cheap, and consumption is few, saves cost and accessory substance is few.
Description
Technical field
The present invention relates to catalyst chemical and field of grease chemical technology, more particularly, to a kind of resistant to elevated temperatures solid of high hydrophobicity
Acid catalyst.
Background technology
Into after 21 century, the emerging field such as oil chemistry and food, the energy is contacted closely, grease esterification, ester exchange etc.
Reaction is the important reaction of many fine chemicals of synthesis, functional grease and biomass fuel, is directed to many of grease
Reaction is big to be required for the participation of acidic catalyst could to complete, product yield and post processing complexity also all with catalyst
Selection is closely related.At present, the acidic catalyst used in industrial production is mostly the relatively inexpensive homogeneous catalysis such as the concentrated sulfuric acid
Agent, such catalyst is easily caused the generation of many side reactions in use, and raw material and production can be especially caused at high temperature
The carbonization of thing, reaction solution blacks, and has had a strong impact on the stability of whole reaction system.Further, since be homogeneous catalytic reaction,
After reaction terminates, catalyst needs to neutralize by alkali and washing step, and this process can produce a large amount of waste liquids, dirt is caused to environment
Dye；Meanwhile, this fluid-like state strong acid is corrosive to reaction vessel, higher to equipment requirement, and the plant maintenance cycle is short, production cost
It is higher.
In view of homogeneous catalyst such as is not readily separated, can not reused at the drawback, in recent years heterogeneous catalysis gradually by
The attention of people, wherein the research about solid acid catalyst is even more to obtain more concern, strong-acid ion exchange resin and solid
Body super acids etc. are found to have preferable catalytic performance.
Strong-acid ion exchange resin is the high-molecular compound of a sulfonic network structure of class band.The solid acid be by
Handing over opposite charges on insoluble three dimensions mesh skeleton, the functional group being connected on skeleton and functional group
Change the part of ion three composition.When it is used as catalyst, accessory substance is few, not etching apparatus, and product postprocessing is relatively simple.
But the skeleton structure of strong-acid ion exchange resin is more fragile, it is impossible to be used in the chemical reaction under higher temperature.
Solid super-strong acid refers to that its surface of solids acidity exceedes a class solid acid of the concentrated sulfuric acid, and it is mainly using certain dense
The two is mixed with and formed by the sulfuric acid of degree and various metal oxide carriers by infusion process, because its acid strength is big, just living
Property it is high the features such as and extremely people pay close attention to, such as Zhou Rujin et al. SO4 2-/ZrO2For catalyst, maleic acid list chaff is catalyzed and synthesized
Alcohol ester, activation temperature is 590 DEG C, and maleic anhydride/furfuryl alcohol mol ratio is 1:1,45 DEG C of reaction temperature, the h of reaction time 2.5,
Catalyst amount is 10 wt.% of total reactant quality, and (Zhou Rujin, Peng Huasong, rather just auspicious is solid for average yield 92.6%
Body super acids SO4 2-/ZrO2Research [J] Speciality Petrochemicals of Synthesis of Monofurfuryl Maleate Over, 2004:7-10).Again
Such as Liu Jun, which is encouraged, to be prepared for using turpentine oil and acetic acid as the TiO of raw material one-step synthesis method terpinyl acetate2/ SO4 2-Zeolite molecules
Sieve catalyst.Test result indicate that, the h of roasting time 4,550 DEG C of sintering temperature impregnates the mol/L of acid concentration 1.0, dip time
20 min, obtained catalyst has stronger catalytic activity, and conversion ratio is 96.3%.（Liu Jun is encouraged, Zheng carefully ring one-step method conjunction
Into the TiO of terpinyl acetate2/ SO4 2-Research [J] Industrial Catalysis of zeolite molecular sieve catalyst, 2008:49-51）.But
The curing mode of such catalyst activity part is the suction-operated using carrier, and active material combination degree is not high, easily stream
Lose, especially easily oozed out in the reaction that polar substances or solvent are participated in from solid phase, lose the advantage of solid catalyst,
Reusing is poor（Kansedo J, Lee K T. Transesterification of palm oil and crude
sea mango (Cerbera odollam) oil: The active role of simplified sulfated
zirconia catalyst[J]. Biomass & Bioenergy, 2012, 40(10):96–104）.In addition, its active matter
The loss of matter can also cause the pollution of reaction product, be not readily separated, the application of solid super-strong acid is very limited.
The content of the invention
It is an object of the invention to provide it is a kind of with product is easily separated, environmentally safe, raw material is cheap, hydrophobicity is strong,
Catalytic activity is high, the repeatable high hydrophobicity high temperature resistant solid acid catalyst utilized.
To achieve the above object, the present invention can take following technical proposals：
High hydrophobicity high temperature resistant solid acid catalyst of the present invention, be using SBA-15 mesopore molecular sieves as carrier, according to
After secondary use phenyltrimethoxysila,e and propyl trimethoxy silicane are modified it twice, then with chlorosulfonic acid carry out sulfonation
Processing produces solid acid catalyst finished product.
Specific preparation principle is shown in Fig. 1：
The first step, prepares SBA-15 mesopore molecular sieves
By P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene), deionized water, 2mol/L mixed in hydrochloric acid, stirring is equal
It is even, then tetraethyl orthosilicate (TEOS) is added dropwise, continue to stir, mix；Then solution is transferred to stainless steel hydrothermal reaction kettle
Middle crystallization.Question response kettle is cooled down, filtering, is washed, is dried at room temperature for deionized water, and gained filter cake is that SBA-15 is situated between
Porous molecular sieve.SBA-15 mesopore molecular sieves rise to 550 DEG C of 6 h of holding in Muffle furnace, can obtain activating SBA- before use
15 mesopore molecular sieves；
Second step, two step modifications are carried out to SBA-15 mesopore molecular sieves
By the SBA-15 mesopore molecular sieves of activation, phenyltrimethoxysila,e, dry toluene is added in reactor, N2Protection
Lower backflow certain time.After after product cooling, filter, and washed with toluene, the solid of gained adds propyl group front three after drying
TMOS, N2Protection lower backflow certain time.Treat that product is cooled down, then filtering is washed, filter cake is placed in toluene with ethanol
Extracted in apparatus,Soxhlet's equipped with absolute ethyl alcohol, remove unreacted silane, remaining solid powder is vacuum dried, obtains
SBA-15 mesopore molecular sieves after modification（SBA-15-ph）；
3rd step：The sulfonation of SBA-15 mesopore molecular sieves is handled
The SBA-15-ph powder that second step is obtained is scattered in dichloroethanes, in N2After protection lower backflow certain time,
Cool down and chlorosulfonic acid is added dropwise under stirring as sulfonating agent, in N2Protection is lower to be continued to flow back, and reaction terminates and cooled down
Afterwards, filter, then washed with ethanol, it is vacuum dried after, can obtain high hydrophobicity solid acid catalyst finished product.The solid acid of gained
Benzene sulfonic acid base load capacity is 0.40-1.15 mmol/g in finished catalyst, and acid amount is 0.36-1.09 meq H+/ g, highest makes
It it is 300 DEG C with temperature.
SBA-15 mesopore molecular sieves are modified twice with propyl trimethoxy silicane using phenyltrimethoxysila,e
When, the weight ratio of SBA-15 mesopore molecular sieves and phenyltrimethoxysila,e is 1:0.6 ~ 3.6, its optimum weight ratio is 1: 3；
The weight ratio of SBA-15 mesopore molecular sieves and propyl trimethoxy silicane is 1:1.6.
Present invention selection, using SBA-15 mesopore molecular sieves as carrier, is due to that SBA-15 mesopore molecular sieves have compared with Gao Bibiao
Area, the meso-hole structure of rule, higher pore volume, higher heat endurance and preferable chemical stability, especially table
Face is rich in oh group, and convenient connection other functions group assigns its Special use performance or carries out functional modification：Use benzene
, can be in its surface grafting phenyl ring when base trimethoxy silane is modified SBA-15 carriers for the first time.Due to the space bit of phenyl ring
Resistance is larger, with reference to hydroxyl limited amount, the carrier surface after modification still retains a large amount of hydrophilic hydroxy groups.Therefore, continuing to use third
Base trimethoxy silane is modified SBA-15 mesopore molecular sieves again, it is therefore intended that is combined residual hydroxyl as far as possible and is introduced
Alkyl, so that the hydrophobicity of catalyst is improved, beneficial to the close of organic molecule.Finally, it will be situated between by the SBA-15 modified twice
Porous molecular sieve carries out sulfonation processing with chlorosulfonic acid, makes the solid acid catalyst of preparation and not only has high temperature resistant and high hydrophobicity work(
Can, and there is strong acidity simultaneously, and then show good catalytic performance.；Simultaneously because its entity is silica knot
Structure, can tolerate higher temperature, and maximum operation (service) temperature is much higher by and current urged with sulfonic solid acid up to 300 DEG C
Agent commercially produced product（Acid cation exchange resin, temperature in use is below 100 DEG C, and temperature is too high will to cause catalyst bone
Frame is collapsed）.
The advantage of solid acid catalyst produced by the present invention be embodied in it is following some：
1st, the catalyst is convieniently synthesized, while modifying SBA-15 molecular sieves, maintains order mesoporous rule
Then structure and higher specific surface area, improve the decentralization of active site, so as to add catalytic efficiency；
2nd, firmly it is strapped in by acidic-group in meso-hole structure, effectively prevent loss of active component, is improved and urge
The stability of agent.Handled by surface hydrophobic, be conducive to the acid catalyzed reaction of organic compound；
3rd, high temperature resistant, hydrophobicity is strong, has a wide range of application, and technological operation is interval wide, is easy to produce control；
4th, non-corrosiveness, it is environmentally safe；
5th, raw material is cheap, and consumption is few, saves cost and accessory substance is few；
6th, the catalyst can be separated using simple filtration method from reaction product, have larger excellent than homogeneous reaction technique
Gesture, improves production efficiency.Remain to keep greater activity after being used repeatedly, it is reusable, reduce production cost.
Brief description of the drawings
Fig. 1 is the preparation principle schematic diagram of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of finished solid acid catalyst of the present invention.
Fig. 3 is the transmission electron microscope picture of finished solid acid catalyst of the present invention.
Fig. 4 is the nitrogen adsorption curve spectrogram of finished solid acid catalyst of the present invention.
Fig. 5 is the infrared spectrum of finished solid acid catalyst of the present invention.
Fig. 6 is the thermogravimetric curve spectrogram of finished solid acid catalyst of the present invention.
Embodiment
More detailed explanation is done to the present invention below by specific embodiment.
Embodiment 1
The first step, prepares SBA-15 mesopore molecular sieves
5 g P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene), the mL of 38 mL deionized waters 150 are added in beaker
2 mol/L hydrochloric acid, stirs 6 h at 40 DEG C, then 10.5 g tetraethyl orthosilicates (TEOS) are added dropwise, and continues to stir 24
H, is mixed.Then, solution is transferred in stainless steel hydrothermal reaction kettle (using polytetrafluoroethylene (PTFE) as liner) crystallization (in 100 DEG C of baking ovens
In) 48 h, question response kettle cooling, filtering, washed and (be repeated 6 times) with deionized water, be dried at room temperature for obtained by filter cake i.e.
For SBA-15 mesopore molecular sieves.SBA-15 mesopore molecular sieves are before use, with 10 DEG C/min heating rate liter in Muffle furnace
To 550 DEG C of 6 h of holding, it can obtain activating SBA-15 mesopore molecular sieves；
Second step, two step modifications are carried out to SBA-15 mesopore molecular sieves
Weigh the SBA-15 mesopore molecular sieves of 1.0 g activation, 0.6 g phenyltrimethoxysila,es, 20 mL dry toluenes
It is placed in together in 100 mL there-necked flasks, N224 h of the lower backflow of protection.After after product cooling, suction filtration is simultaneously washed, gained with toluene
Solid dry after be placed in again in 100 mL there-necked flasks, then add 1.6 g propyl trimethoxy silicanes, N2Protection is next time
Flow 12 h.Treat that product is cooled down, suction filtration is simultaneously placed in extracting in the apparatus,Soxhlet's equipped with absolute ethyl alcohol after wash with toluene and ethanol
6 h, to remove unreacted silane, remaining solid powder is dried in vacuo 12 h at 80 DEG C, the SBA- after being modified
15 mesopore molecular sieves（SBA-15-ph）；
3rd step：Sulfonation processing is carried out to SBA-15 mesopore molecular sieves
The SBA-15-ph powder that 1.0 g second steps are obtained is scattered in 25 mL dichloroethanes, in N2Protection is next time
Flow after 1 h, cool down and 10 mL chlorosulfonic acids are added dropwise under stirring as sulfonating agent, then in N2Protection is lower to be continued back
Flow 5 h.After reaction terminates and cooled down, suction filtration, then washed 3 times with 20 mL ethanol, it is dried in vacuo after 10 h, obtains at 110 DEG C
To high hydrophobicity solid acid catalyst finished product.Through measurement, finished catalyst（It is designated as 1#）Benzene sulfonic acid base load capacity be 0.40
Mmol/g, 0.36 meq H of acid amount+/g。
Modify the consumption of the phenyltrimethoxysila,e used by SBA-15 mesopore molecular sieves in increase second step for the first time successively,
Label 2# ~ 6# finished catalyst is can obtain, its load capacity and acid amount see the table below 1.
Influence of the different phenyltrimethoxysila,e consumptions of table 1 to catalyst loadings and acid amount
It can be seen that from upper table, when phenyltrimethoxysila,e consumption is 3.0 g, obtained finished catalyst（5#）Benzene
Sulfonic group load capacity and acid amount highest.
Finished catalyst（5#）Scanning electron microscope (SEM) photograph see Fig. 2.It can be seen that from ESEM：Finished catalyst of the present invention
Microcosmic appearance it is close with the microcosmic appearance of SBA-15 molecular sieves, in typical wheat head shape.
Finished catalyst（5#）Transmission electron microscope picture see Fig. 3.The catalysis is clear that from its transmission electron microscope picture
The regular duct uniformly arranged, shows SBA-15 carriers in surface modification and sulfonation process, its microscopic appearance inside agent
Do not destroyed, with good structural stability.
Finished catalyst（5#）Nitrogen adsorption curve see Fig. 4.It is seen that the nitrogen adsorption capacity of the catalyst is
560 cm3/ g, aperture size concentrates on 6-7 nm, can be obtained after being calculated through BET, and the specific surface area of the solid acid catalyst is 545
m2/ g, compared to the conventional solid acid catalyst using metal oxide as carrier（Such as sulfuric acid loaded zirconia solid acid catalyst
Specific surface area is 30-50 m2/g）, the present invention in finished catalyst have the aperture of size uniformity, larger pore volume with than surface
Product, thus the contact probability of active material and reaction mass is added, therefore reactivity is high.
Finished catalyst（5#）Infrared absorpting light spectra see Fig. 5.Such as infrared absorpting light spectra（Fig. 5）It is shown, the finished product
Catalyst is in 654 cm-1Place has faint new absworption peak to occur, and this can be attributed to C-S stretching vibration.Two faint suctions
Receive peak and appear in 3080 cm-1With 3054 cm-1 Place, this is due on phenyl ring=stretching vibrations of CH keys causes, and 1572
cm-1With 1480 cm-1Absworption peak at two can be attributed to the vibration of phenyl ring skeleton.2900 cm-1The absorption of both sides can be with
It is attributed to the vibration of C-C keys on propyl group.In addition, 1172 and 1065 cm in the infrared spectrum of the catalyst-1Absorption signal can
To be attributed to the stretching vibration of S=O in sulfonic group, and 3430 cm-1The broad absorption band at place and 1634 cm-1Absworption peak（OH's
Stretching vibration）Also all it is sulfonic group (- SO3H presence) provides admissible evidence.Above-mentioned infrared spectrum shows phenyl trimethoxy
Silane has successfully been bonded on SBA-15 carriers with propyl trimethoxy silicane, and is successfully carried out on the phenyl ring of connection
Sulfonating reaction.Moreover, using in the infrared spectrogram of rear catalyst, sulfonic group (- SO3H characteristic IR absorbance peaks) are also obvious
Present, illustrate that catalytic activity group does not change.
Finished catalyst（5#）Thermogravimetric curve see Fig. 6.It can be seen that the catalyst is when persistently overheating,
Its thermal weight loss is divided into two sections：Thermal weight loss below 150 DEG C is the evaporation for combining water, and 350 DEG C -700 DEG C of thermal weight loss is activity
Caused by the oxidizing process of material.In addition, it can be seen that the oxidizing process of acitve organic matter matter is from 300 in fact from DTG curves
DEG C when start, when less than 300 DEG C the active material of the catalyst is relatively stable.Convention acidic cationic ion-exchange resin is general
Can only be used below at 100 DEG C, temperature is too high will to cause catalyst backbone to collapse, and in the present invention solid catalyst tolerance temperature
Degree is higher by much than it.
Embodiment 2
Application of the solid acid catalyst of the present invention in acidolysis reaction：
50 mL round-bottomed flasks are placed in after 2.00 g soybean oils, 1.66 g octanoic acids are mixed with 1.98 g capric acid, first will
Reaction substrate is dried in vacuo 1 h to remove water micro in reaction substrate at 80 DEG C, is then respectively adding the preparation of embodiment 1
Label 1# ~ 6# the g of finished solid acid catalyst 0.28, then reactant mixture is placed in oil bath pan is heated to 160 DEG C, in nitrogen
10 h are reacted under gas shielded；After acidolysis reaction terminates, solid catalyst is separated by filtration, then reactant mixture is dissolved in into 30 mL
N-hexane simultaneously moves into separatory funnel.Then, the mol/L of 100 mL 0.8 KOH (30% ethanol) solution is added, it is strong to shake,
Water alcohol phase is removed, then after upper strata hexane is washed again with saturation NaCl solution, is dried, finally steamed with anhydrous sodium sulfate
Distillation goes n-hexane to obtain middle long-chain fat acid lipid, and wherein medium-chain fatty acid Percentage bound is determined with gas chromatography（GB/T
17377-2008）.
The acidolysis reaction of soybean oil and medium chain fatty acid is carried out with label 1# ~ 6# finished solid acid catalyst respectively, instead
Catalyst activity relatively see the table below 2 in answering.
The activity of the finished solid acid catalyst of table 2
Find out from upper table, 5# finished catalysts have higher acid-decomposed activity, under the catalyst action, have it is more in
Chain fatty acid（Percentage bound is up to 80.5 wt.%）It is attached in grease molecules.In addition it is also possible to according to medium chain fatty acid in grease
The specific demand of ratio, selects different types of catalyst and different material rates to carry out the acidolysis reaction of grease, so that
To the middle long chain fatty acids biodiesel product of different proportion, the need for meeting different purposes.
Embodiment 3
Reusing test of the 5# finished solids acid catalyst in acidolysis reaction in the embodiment of the present invention 1：
50 mL round-bottomed flasks are placed in after 2.00 g soybean oils, 1.66 g octanoic acids are mixed with 1.98 g capric acid, first will
Reaction substrate is dried in vacuo 1 h to remove water micro in reaction substrate at 80 DEG C, then adds 5# prepared by embodiment 1
The g of solid acid catalyst 0.28, then reactant mixture is placed in oil bath pan is heated to 160 DEG C, 10 are reacted under nitrogen protection
h；After solid catalyst is separated by filtration, then washed respectively 3 times with n-hexane and ether.Exist by the solid acid catalyst of washing
It is dried in vacuo at 110 DEG C after 10 h, the lower batch acidolysis reaction of input（It is identical when reaction condition with using first）, so this is urged
Agent is reused 5 times（When catalytic amount is not enough, catalyst make-up is reclaimed with parallel test）.Acidolysis reaction product postprocessing
Method and medium chain fatty acid assay method be the same as Example 2.
The activity that solid acid catalyst produced by the present invention reuses five times is shown in Table 3.
Table 3：Solid acid catalyst circulating repetition utilizes test result
As can be seen from Table 3, in the present invention solid acid catalyst in soya-bean oil with octanoic acid, in the acidolysis reaction of capric acid through 5 weights
Activity remains at more than 83% after multiple utilization, illustrates that the catalytic stability of the catalyst is high, can connect in intermittent reaction device
It is continuous to use.
Claims (2)
1. a kind of high hydrophobicity high temperature resistant solid acid catalyst, it is characterised in that：The solid acid catalyst is situated between with SBA-15
Porous molecular sieve is carrier, after being modified twice it using phenyltrimethoxysila,e and propyl trimethoxy silicane successively,
Sulfonation processing is carried out with chlorosulfonic acid again and produces benzene sulfonic acid base load in solid acid catalyst finished product, the solid acid catalyst finished product
Measure as 0.40-1.15mmol/g, acid amount is 0.36-1.09meqH+/ g, maximum operation (service) temperature is 300 DEG C；Using phenyl trimethoxy
When base silane is modified the SBA-15 mesopore molecular sieves twice with propyl trimethoxy silicane, SBA-15 mesopore molecular sieves
Weight ratio with phenyltrimethoxysila,e is 1:The weight of 0.6 ~ 3.6, SBA-15 mesopore molecular sieve and propyl trimethoxy silicane
Amount is than being 1:1.6.
2. high hydrophobicity solid acid catalyst according to claim 1, it is characterised in that：Using phenyltrimethoxysila,e
When modifying for the first time SBA-15 mesopore molecular sieves, the weight ratio of SBA-15 mesopore molecular sieves and phenyltrimethoxysila,e is
1:3。
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| CN110627086B (en) * | 2018-06-25 | 2021-12-21 | 中国石油化工股份有限公司 | Preparation method of organic functional group functionalized SBA molecular sieve |
| CN113398991A (en) * | 2021-05-26 | 2021-09-17 | 华东理工大学 | Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst |
| CN115999638A (en) * | 2022-12-21 | 2023-04-25 | 浙江中硝康鹏化学有限公司 | Immobilized trifluoromethyl sulfonic acid and preparation method thereof |
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Effective date of registration: 20200827 Address after: 450100 southwest corner of intersection of Jianshe Road and Industrial Road, Zhengzhou, Xingyang, Henan Patentee after: Henan Zhengtong Food Technology Co.,Ltd. Address before: 450001 No. 100 Lianhua street, hi tech Development Zone, Henan, Zhengzhou Patentee before: HENAN University OF TECHNOLOGY |